Process for producing stable aqueous dispersions of polymer containing plasticizers therefor



Patented Nov. 20,1951

UNITED STATES PATENT OFFICE PROCESS FOR PRODUCING STABLE AQUE- OUS DISPERSIONS F POLYMER CON-.'

TAINING PLASTICIZERS THEREFOR Egbert Oornelis Hendrik Kolvoort, Amsterdam, Netherlands, assignor to Shell Development Company, San Francisco, Calif., a corporation of Delaware No Drawing. Application filed February 8, 1949, Serial No. 75,312. In the Netherlands February 5 Claims.

ticles.

easily upon being agitated.

very small.

while stirring vigorously. In this prior method, which are so small that the homogeneity of the it is necessary that the heating and stirring be dispersion is not disturbed en after long storcontinued until the plasticizer has been absorbed App r n ly he iffu process y w h or combined with the polymer particles since he p asti r s gradually t p rted from the otherwise the plasticizer tends to separate. plasticizer p s o e P y Particles h Unlike the prior method, the process of the reduction i e of he droplets is ch f ster present invention enables production of aqueous than the e ixing or creaming p e dispersions which possess exceptional stability qu t y, the combined dispersion on to ge is even though the plasticizer is present therein as converted into a dispersion of Diastioized P ym r particles or droplets which are separate and disparticles with correspond pp ce of tinct from the polymer particles. If desired, the separate plastic r P however, the dispersions from the method of the dispersion is Still more S than the u o invention may have the plasticizer partly or enof p c r in Waterir ly absorbed into the suspended polymer par- Any of the substantially water-insoluble plasti- The new method is particularly advanc e s e p oy with res ous po ymers are suit-- tageous because these objects of the invention are this for use in the process. such as those s e achieved without heating and with little or no compounds ilin ve 200 C- Which are comagitation, the latter being important since some n e with the pa ticu p y P rably. polymer suspensions tend to coagulate rather the plasticizer is liquid at the normal p ture at which the jelly is prepared, this usually According to the process of the invention a being at about 20 C. though it may be in t jelly or jelly-like mixture is prepared by mixing range of about C- to C- In those cases without heating the plasticizer in liquid condition Where it s esired to e p oy a plasticizer which with a small quantity of a concentrated aqueous s solid at normal temperatures. e je y is presolution of an emulsifier. Upon dilution of the pared therefrom by using the plasticizer in o formed jelly with water, emulsified plasticizer is liquid condition obtained by incorporating it with obtained having the droplets in an extremely flne sufllcient water-insoluble liquid solvent such as state of subdivision. By eil'ecting the dilution benzene or toluene or another normally liquid directly with an aqueous dispersion of po y er, PloStioiZer- The y s and number of plasticizer! there is obtained the desired dispersion of polyin the plestieizerelt Su e for use With thie mer containing emulsified plasticizer therein. 46 process are large and include such representative The use of the jelly according to the present compounds as bll y Dhtheiete, diootyl p invention offers considerable advantages. The ate, di(Z-ethylhexyl) phthalate, dibutyl sebacato, degree of dispersion of an emulsion prepared by dibenzyl Dhtholote, diootyl edlpote. triethylene the jelly method is extremely high; that is to'say yco d ot diootyl t c o ted the particles of plasticizer in the emulsion are 50 diphenyl, triphenyl phosphate, tricresyl phos- Consequently, the emulsion is exphate, 2mitrodiphenyl, diethoxy ethyl phthalate, ceptionally stable. While it might be possible to dlcyclohexyl'phthalate, etc. Either single plastiprepare an emulsion having the same particle size cizer compounds may be used or combinations by very intensified agitation using mechanical thereof in any number. In some cases, it is demeans such as a colloid mill, the method of the invention is for simpler and cheaper. Moreover. an emulsion prepared from a jelly shows less variety in particle size than an emulsion of about the same degree of dispersion prepared by mechanical means because in the former the particles are more uniform in size. The conventional method gives an emulsion containing a considerable proportion of particles which are of larger size than the average on the whole. Consequently, the emulsion prepared by the old method, even if very vigorous mechanical agitation is employed, gives a product which is less stable than that from the method of the invention.

The jelly method gives plasticizer particles The combined sirable to employ high-boiling aromatic petroleum extracts or chlorinated paramns either alone or with other true plasticizers.

In forming the jelly there is used an aqueous solution of an emulsifier containing about to 70% emulsifier therein, although solutions of about 30% to 60% concentration are preferred. Any of the various emulsifiers well known in the art are suitable such as, for example, soaps like sodium or potassium myristate, laurate, pa1mitate, oleate, stearate, rosinate or hydroabietate; or alkali metal alkyl or alkaline sulfates or sulfonates including sodium or potassium lauryl sulfates, oleyl sulfate, cetyl sulfate, stearyl sulfonate, sulfonated Turkey red oil, sulfonated mineral oi s sodium alkyl naphthalene s' li'onate, sodium alkyl aryl sulfonate, etc.; aswell as ammonium salts of such sulfates or sulfonates such ascetyl trimethyl ammonium bromide, cetvi pyridinium bromide, sorbitol monolaurate. sorbitol monooleate, polyoxyalkylene ethers of partial esters of sorbitol with lauric, palmitic, stearic or oleic acid. Particu arly su ted for the invention are the salts of alkyl sulfonates wherein the'alkyl groups contain about to carbonatoms. Such roducts are obtainable by known methods of subjecting parafflnic or cyclonaraflinic hydrocarbon mixtures which are substantially free from aromatic hydrocarbons to reaction with sulfur dioxide and chlorine, and neutralizing the obtained sulfur chloride with a base such as sodium or potassium hydroxides. Other we l suited emu sifiers are sodium alkyi sulfates obtained by sulfating oleflns of 10 to 20 carbon atoms from cracked petroleum wax and forming the sodium salts thereof.

of the jelly employed in the process of the invention.

Example I Jellies were prepared by adding di-(2-ethylhexyl) phthalate to concentrated aqueous solutions of various emulsifiers. The dioctyl phthalate was admixed gradually while the mixture was slowly stirred. The emulsifiers. proportions and concentrations of the materials used in forming the jellies are tabulated below:

er Ce t r Cent Emulsifier Dioctvl A" Phth 'late Emulsiiler in Solution in Jelly Sodium alkyl sulfonate Do I morgue Hornholin nleate Sodium alkyl sulfate L 1 Product from su fochlorination of 10 to 18 carbon atoms aromatichec pe roleum fraction, followed by saponiiication of resulting sulfooh nride with caustic.

LPI'oduct from cracked petroleum wax oleilns of 10 to 18 carbon Example If tricresyl phosphate to a stirred aqueous solution of the emulsifier containing 43% emulsifier. The formed jelly contained about 90% of tricresyl phosphate.

Example 11'! Mixture of tricresyl phosphate and dioctyl phthalate were employed to prepare jellies thereof wherein an aqueous solution containing 29% of the sodium alkyl sulfonate obtained by saponification of the product of cm to Cu; aromatic petroleum fractions was used. Each jelly contained 92% of the mixture of esters, in one the mixture consisting of tricresyl phosphate and 20% dioctyl phthalate, and the other consisting of 67% tricresyl phosphate and 33% dioctyl phthalate.

Example IV In order to prepare a jelly of triphenyl phosphate (melting point 52 C.), a mixture thereof with 33% added benzene, or 33% added dioctyl phthalate wa prepared, each of which was liquid at room temperature. Using abouta 30% aqueous solution of the emulsifier described in Example II. there were obtained jellies from each mixture which contained about of the mixtures.

Example V Jellies were prepared from the cresyl ester of toluene sulfonic acid. In the first, a jelly containing 89% of the ester was obtained with use of an aqueous solution containing 41% of the sodium alkyl sulfate described in Example I. Jellie were also obtained using an aqueous solution containing 30% of sodium alkyl sulfonate prepared by saponification of the sulfochlorides of a Cio-C1a non-aromatic petroleum fraction. These contained 10, 20 and 33% dioctyl phthalate in admixture with the cresyl ester, the jelly in each case containing 92% of the mixture of esters.

Upon diluting the jelly of pasticizer with water, an aqueous emulsion i obtained wherein water becomes the continuous phase and the plasticizer is contained therein in an extremely finely divided and uniform state of subdivision. If desired, the jelly may be diluted with water alone to obtain an emulsion which is then admixed with the aqueous dispersion of polymer. Preferably, the dilution of the jelly is effected directly with the aqueous dispersion of polymer so that the desired product may be obtained in a single operation.

The dilution may be eifected in any suitable manner. Thus, the diluent may be added to the jelly-like mixture all at once, in portions or continuously. Conversely, the jelly-like mixture may be added to the diluent along the same lines. In general, it is preferable to add the diluent to the jelly-like mixture gradually with agitation until water becomes the continuous phase. In this manner, there is continuously maintained a substantially homogeneous mixture owing to the agitation secured by the mild stirring and the graduated introduction of the diluent. If care is not taken during the early stages of the dilution, there may be formation of lumps which may require more violent agitation or kneading to break up in order to obtain dispersion of the plasticizer. After the initial formation of a continuous water phase, the remainder of the diluent may be added rapidly without undue care. In practice, it is preferable to effect the dilution by stirring vigorously or causing turbulence with the aid of a turbo-mixer or centrifugal pump. If it is desired to conduct the dilution continuously, it is advantageous to inject a stream or streams of amuse ticles therein are in finely divided condition and are suspended in the aqueous medium containing an aforementioned emulsifier so that some coagulation procedure is necessary to separate the polymer from the medium. The polymer is of such character as to be solid at normal temperature of about C. The emulsified suspension is obtained by homopolymsrizatlon or copolymerization of any polymerizable olefinic compound, especially those containing a vinylidine group The polymerizable compounds which form resinous polymer by addition polymerization involving carbon-to-carbon bonding through olefinic carbon atoms include vinyl halides like vinyl chloride or bromide; vinyl esters such as vinyl acetate, propionate or butyrate; vinylidene chloride or bromide; vinyl aromatic compounds like styrene, methyl styrene and chlorostyrene; acrylate and methacrylate esters like methyl, ethyl or butyl acrylate or methacrylate; unsaturated nitriles such as acrylonitrile and methacrylonitrile; vinyl ketones such as methyl vinyl or methyl isopropenyl ketone; allyl compounds such as allyl chloride as well as similar singly olefinic compounds. Also suitable are compounds which contain a plurality of olefinic linkages between aliphatic carbon atoms that are adapted to enable formation of addition polymers as is the case with butadiene-1,3, isopropene, 2,3-dlmethyl butadiene- 1.3, chloroprene, divinyl benzene, Z-methyl penta- (Ilene-2,4, 2-methyl pentadien-IB, ethylene glycol dimethacrylate, diallyl phthalate, diallyl di lycolate, allyl vinyl phthalate, diallyl maleate. diallyl fumarate, diallyl ether of ethylene glycol, triallyl ether of glycerol, and similar compounds as well a their homologs. Copolymers can be prepared by use of mixtures of one or more of the polymerizable compounds, the mixture containing at least an appreciable proportion of any one of the compounds, 1. e. at least 1% of a second, third or fourth compound. For example, vinyl chloride can be mixed with 5% to of vinyl acetate, and, if desired, 1% to 5% of divinyl benzene can be present as third constituent.

The aqueous suspension of emulsified polymer may contain any desired concentration of polymer. Ordinarily, it is preferred to employ concentrated mixtures containing about to 6 polymer, although more dilute mixtures may be employed if desired.

The proportion of jelly-like mixture and aqueous dispersion of polymer is ordinarily so chosen that the resulting mixture contains about 0.1 to 1.5 parts by weight of plasticizer per part of polymer. The choice of the ratio of plasticizer to polymer is governed primarily by the properties desired in the ultimately deposited mixture of plasticized polymer. With many polymers, including polyvinyl chloride, it is preferred to employ such amounts of the jelly and polymeric per part of polymer is present. The particular proportions of jelly and aqueous dispersion of f polymer are, of course, dependent upon the congradually became scarcer.

centrations of plasticizer and polymer in their respective mixtures.

The following examples illustrate the process of the invention in detail and point outsomc advantages thereof.

Example VI The emulsifier used was a mixture of sodium alkyl sulfonates consisting of about 65% of monosulfonates and about 35% disulfonates obtained by sulfochlorination of a mixture of saturated hydrocarbons, the constituents of which contained about 12 to about 18 carbon atoms, the average .number being about 15, followed by saponification of the resulting sulfochlorides with sodium hydroxide. In 82 kg. of a 33.5% by weight solution of the emulsifier 6.9 kg. of sodium bicarbonate were dissolved. About 560 kg. of dioctyl phthalate were gradually added while stirring, thereby causing formation of a jelly-like mass. About three minutes time passed in add-' ing the dioctyl phthalate to the emulsifier solution. The jelly-like mixture was then mixed with 2800 kg. of a 60% by weight aqueous suspension of polyvinyl chloride and the mixture stirred until a homogeneous dispersion had been obtained. The dispersion prepared in this manner was marked by very high stability. After months of storage, there was no trace of creaming therein. Microscopic investigation showed that the size of the emulsified plasticizer particles had gradually decreased during storage, although at first the particles in the microscopic picture were visible in all sizes, i. e., from the limit of the dispersing picture up to 4 mu, the particles from 3 to 4 mu It should be noted that the polymer particles are smaller by one order of magnitude so that they are too minute to be seen under the microscope.

Example VII The experiment of Example VI was repeated with the exception that only half the quantity was used. The dispersion obtained was very much like that of Example VI and was also marked by high stability.

Example VIII An aqueous suspension of polyvinyl chloride of 60% concentration by weight was mixed with a jelly-like mixture consisting of dioctyl phthalate and a 35% aqueous solution of the emulsifier described in Example VI. The ratio by weight of polyvinyl chloride and dioctyl phthalate amounted to 3: 1 while the ratio by weight of dioctyl phthalate and emulsifier (dry substance in the jelly) was 19:1. To the resulting polymer, plasticizer dispersion about 0.2% by weight of sodium bicarbonate was added.

The microscopic picture of the freshly prepared dispersion showed particles of 2 to 4 mu and the dispersion was stable. The dispersion was grad ually heated in an autoclave C., which temperature was attained after 1 hours. Subsequently, microscopic investigation revealed that the particles were generally not larger than 1 mu.

Another quantity of the dispersion prepared at room temperature according to this example was heated at C. for 5 minutes. When seen under the microscope, the largest particles measured 1 to 2 mu.

If desired, the jelly-like mixture or plasticizer may also contain heat and light stabilizers for the polymer and/or colorants for incorporation into the final aqueous dispersion. Thus, there may be incorporated such materials which pro mote chemical stability oi the polymer particularly halogen-containing polymers like naphthyl glycidyl ether, resorcinol diglycidyl ether, bisphenol diglycidyl ether, diphenyl urea, sodium bicarbonate and the like. The colorants which are soluble in oil and the plasticizer include anthraquinone colors, acetamine colors and celanthrene colors. There also may be incorporated various pigments such as lead white, lithopone, titanium dioxide, lead chlorinate, lead xide, antimony oxide and the like. The stable aqueous dispersions containing the plasticizer, and, if desired, stabilizer and/or colorants, are particularly suitable for various technical applications such as the production of voils, waterproofing of paper or fabrics by soaking these materials in the dispersions or covering them therewith, treating the fabrics to render them noncreasing, etc. If so desired, thickening agents such as casein, methyl cellulose and various other like substances may also be added to the dispensions for the above purposes. I

As pointed out before, the storage of dispersions of polymers and plasticizers prepared according to the invention results in the plasticizer being gradually absorbed by the polymer. This absorption may be hastened by heating. Any temperature between room temperature and 100 C. may be applied and, if desired, temperatures exceeding 100 C. may be utilized provided the dispersion is maintained under pressure so as to prevent boiling away of the water therefrom. In general, the higher the temperature, the quicker the process of absorption. In some cases, this heating results in increase of the stability of the dispersion.

I claim as my invention:

1. A process for the production of an aqueous dispersion of solid resinous polymer containing a plasticizer for said polymer, said plasticizer being a substantially water-insoluble ester compatible with said resinous polymer and boiling above 200 C., which comprises mixing a predominant proportion of said plasticizer in liquid condition with a small quantity of an aqueous solution containing a substantial proportion of an emulsifying agent so as to thereby form a jellied mixture, and then mixing suiiicient of an emulsified aqueous suspension ofdispersed particles of said solid resinous polymer with said jellied mixture so that an aqueous emulsion is formed wherein water constitutes the continuous phase.

2. A process for the production of an aqueous dispersion of resinous polymer of a compound containing a vinylidene group, said dispersion containing a compatible plasticizer for said polymer which is a substantially water-insoluble ester having a boiling point above 200 C., which comprises mixing said ester in liquid condition with about 3% to 20% of an aqueous solution contain ing about 5% to 70% of an emulsifying agent so that a jellied mixture is formed, and then adding with mixing an emulsified aqueous suspension of dispersed particles of said solid resinous polymer containing about 30% to 60% polymer to said jellied mixture, the proportions of said suspension and said jellied mixture being such that when the two are mixed, water constitutes the continuous phase thereof and there is 8 present therein about 0.1 to 1.5 parts by weight of said ester per part of said polymer.

3. A process for the production of an aqueous dispersion of a polymer of vinyl chloride contain ing a substantially water-insoluble dialkyl ester of a dicarboxylic acid which is compatible with said polymer, is a liquid at 20 C., and has a boiling point above 200 C.,'which comprises mixing said ester with about 10% to 15% of an aqueous solution containing about 80% to 60% of sodium alkyl sulfonate having 10 to 20'carbon atoms in the alkyl group thereof whereby a iellied mixture is formed, and then adding gradually at least until water becomes the continuous phase of the mixture while agitating an emulsified aqueous suspension of dispersed particles of said polymer,

which is solid and substantially insoluble in water, to said jellied mixture, the proportion of said suspension and said jellied mixture being such that in the final mixture thereof there is present about 0.2 to 1 part by weight of said ester per part of said polymer.

4. A process for the production of an aqueous dispersion of polyvinyl chloride containing dioctyl phthalate which comprises mixing to homogeneity said ester with about 10% to 15% of an aqueous solution containing about to 60% of sodium alkyl sulfonate having 10 to 20 carbon atoms in the alkyl group thereof and thereby forming a jellied mixture, and then adding an emulsified aqueous suspension of dispersed particles of polyvinyl chloride containing about 30% to 60% of said polymer to said jellied mixture, the addition being eflected gradually with agitation at least until water becomes the continuous phase, and the proportion of said suspension and said iellied mixture being such that there is present in the final mixture about 0.2 to 1 part by weight of said ester per part of said polymer.

5. A process for the production of an aqueous dispersion of polyvinyl chloride containing dioctyl phthalate which comprises mixing to homogeneity said ester withabout 10% to 15% of an aqueous solution containing about 30% to 60% of sodium alkyl sulfate having 10 to 20 carbon atoms inthe alkyl group thereof and thereby forming a jellied mixture, and then adding an emulsified aqueous suspension of dispersed particles of polyvinyl chloride containing about 30% to 60% of said polymer to said jellied mixture, the addition being eflected gradually with agitation at least until water becomes the continuous phase, and the proportion of said suspension and said jellied mixture being such that there is present in the final mixture about 012 to 1 part by weight of said ester per part of said polymer.

EGBERT CORNELIS HENDRIK KOLVOORT.

REFERENCES CITED The following references are of record in the 

1. A PROCESS FOR THE PRODUCTION OF AN AQUEOUS DISPERSION OF SOLID RESINOUS POLYMER CONTAINING A PLASTICIZER FOR SAID POLYMER, SAID PLASTICIZER BEING A SUBSTANTIALLY WATER-INSOLUBLE ESTER COMPATIBLE WITH SAID RESINOUS POLYMER AND BOILING ABOVE 200* C., WHICH COMPRISES MIXING A PREDOMINANT PROPORTION OF SAID PLASTICIZER IN LIQUID CONDITION WITH A SMALL QUANTITY OF AN AQUEOUS SOLUTION CONTAINING A SUBSTANTIAL PROPORTION OF AN EMULSIFYING AGENT SO AS TO THEREBY FORM A JELLIED MIXTURE, AND THEN MIXING SUFFICIENT OF AN EMULSIFIED AQUEOUS SUSPENSION OF DISPERSED PARTICLES OF SAID SOLID RESINOUS POLYMER WITH SAID JELLIED MIXTURE SO THAT AN AQUEOUS EMULSION IS FORMED WHEREIN WATER CONSTITUTES THE CONTINUOUS PHASE. 